JP2014177017A - Decorative sheet and decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet and a decorative material each endowed, even in a case of being subjected to an embossing work employing infrared heat and pressure impressed by an embossing plate, with excellent heat storage and emboss imprinting capacities while securing abrasion resistance, transparency, and heat resistance.SOLUTION: The provided decorative sheet and decorative material are each a decorative sheet and the like possessing, in proper order atop a patterned layer 3, at least a transparent resin layer 5 and a surface protective layer 6 wherein (1) the thickness of the transparent resin layer is at least 120 μm, wherein (2) the transparent resin layer includes at least one type of infrared absorbent selected from the group consisting of antimony-doped tin oxide and indium-doped tin oxide, wherein (3) the content of the infrared absorbent with respect to 100 pts.mass of the resin component constituting the transparent resin layer is 1-20 pts.mass, and wherein (4) the outermost layer side thereof is imprinted with an emboss pattern.

Description

  The present invention relates to a decorative sheet and a decorative material.

  Conventionally, as a decorative sheet excellent in abrasion resistance and scratch resistance, for example, a decorative sheet in which a transparent resin layer is formed on a pattern layer is known. In particular, for floor decorative sheets that require high wear properties, it is generally known to increase (increase) the thickness of the transparent resin layer.

  However, when the layer thickness of the transparent resin layer is increased, when embossing is performed after the entire decorative sheet is softened by heating with infrared rays (heat rays), the infrared rays pass through the transparent resin layer. For this reason, since the entire decorative sheet has insufficient heat storage, it cannot be softened by the infrared rays, and as a result, there is a problem that it is difficult to obtain excellent emboss formability (emboss fastness).

  Also, there is a method of transferring an uneven pattern to an uncured surface protective layer by forming an uncured surface protective layer on a transparent resin layer and bonding a shaped film having an uneven pattern to the surface protective layer. It has been proposed (Patent Document 1). In this method, a decorative sheet having a design with a concavo-convex pattern is obtained by curing the surface protective layer after the concavo-convex transfer. However, with this method, it is not possible to mold an uneven pattern deeper than the thickness of the surface protective layer. Therefore, there exists a problem that the designability by an uneven pattern is inadequate.

  As a method for solving these problems, a method in which an infrared absorber is contained in a transparent resin layer has been proposed (Patent Document 2). In this method, since the infrared ray can be efficiently absorbed by the transparent resin layer, the entire decorative sheet can be softened. As a result, excellent embossing moldability is obtained. However, it is difficult to obtain the desired transparency with the infrared absorber, and there is a problem that the heat resistance of the entire decorative sheet is lowered when an excessive amount of the infrared absorber is contained in order to increase the infrared absorption efficiency.

  Therefore, even when embossing is performed by heating with infrared rays and pressing with an embossing plate, a decorative sheet excellent in heat storage and embossing moldability while ensuring wear resistance, transparency and heat resistance, and Development of cosmetic materials is desired.

JP 2011-073146 JP 2000-185370 A

  Even if embossing is performed by heating with infrared rays and pressing with an embossing plate, the present invention ensures makeup resistance, transparency and heat resistance, and is excellent in heat storage and embossing moldability. An object is to provide a sheet and a decorative material.

  As a result of intensive studies to achieve the above object, the present inventor has specified a specific infrared absorber in a transparent resin layer having a specific thickness, and then specified the layer structure of the decorative sheet. In the case of a configuration, the present inventors have found that the above object can be achieved and have completed the present invention.

That is, the present invention relates to the following decorative sheet and decorative material.
1. a decorative sheet having at least a transparent resin layer and a surface protective layer in order on a pattern layer,
(1) The thickness of the transparent resin layer is 120 μm or more,
(2) the transparent resin layer contains at least one infrared absorber selected from the group consisting of antimony-doped tin oxide and indium-doped tin oxide;
(3) The content of the infrared absorber is 1 to 20 parts by mass with respect to 100 parts by mass of the resin component constituting the transparent resin layer,
(4) Embossed pattern is formed on the outermost layer side,
A decorative sheet characterized by that.
2. A base material layer is formed on the back of the pattern layer,
The thickness of the transparent resin layer is at least twice the thickness of the base material layer,
The decorative sheet according to Item 1.
3. The decorative sheet according to item 1 or 2, wherein the resin component constituting the surface protective layer is an ionizing radiation curable resin.
4. The decorative sheet according to any one of items 1 to 3, wherein the surface protective layer contains at least one infrared absorber selected from the group consisting of antimony-doped tin oxide and indium-doped tin oxide.
5. The decorative sheet according to any one of Items 1 to 4, wherein the resin component constituting the transparent resin layer is an olefin resin.
6. A decorative material obtained by laminating the decorative sheet according to any one of items 1 to 5 on an adherend.

  Hereinafter, the decorative sheet and the decorative material of the present invention will be described.

≪Makeup sheet≫
The decorative sheet of the present invention is a decorative sheet having at least a transparent resin layer and a surface protective layer in this order on the pattern layer,
(1) The thickness of the transparent resin layer is 120 μm or more,
(2) the transparent resin layer contains at least one infrared absorber selected from the group consisting of antimony-doped tin oxide and indium-doped tin oxide;
(3) The content of the infrared absorber is 1 to 20 parts by mass with respect to 100 parts by mass of the resin component constituting the transparent resin layer,
(4) Embossed pattern is formed on the outermost layer side,
It is characterized by that.

  The decorative sheet of the present invention has a specific layer structure after containing a specific amount of a specific infrared absorber in a transparent resin layer having a specific thickness. Therefore, even when embossing is applied to the decorative sheet by heating with infrared rays and pressing with an embossing plate, it ensures heat storage and embossability while ensuring wear resistance, transparency and heat resistance. Excellent.

The layer structure of the decorative sheet is not particularly limited as long as it has at least a transparent resin layer and a surface protective layer in order on the pattern layer. For example,
(1) A configuration in which a pattern layer, a transparent adhesive layer, a transparent resin layer, a primer layer, and a surface protective layer are sequentially laminated on a base material layer,
(2) A structure in which a transparent adhesive layer (primer layer), a transparent resin layer, a primer layer, and a surface protective layer are sequentially laminated on the pattern layer.
(3) A configuration in which a backer layer is further laminated on the back surface of the base material layer, with respect to the configuration of (1)
(4) A configuration in which a heat seal layer is further laminated on the back surface of the pattern layer with respect to the configuration of (2) above,
Etc.

  Hereinafter, as a specific description of the layer configuration, the layer configuration (3) will be exemplified and described.

A base material layer may be formed on the back surface of the base material layer pattern layer.

  Although it does not limit as a base material layer, the base material sheet which contains polyolefin resin as a resin component is preferable. Essentially, a sheet made of polyolefin resin is used.

  It does not specifically limit as polyolefin resin, What is normally used in the field | area of a decorative sheet can be used. For example, polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer, polyolefin-based thermoplastic elastomer, etc. Is mentioned. Among these, polypropylene, polyolefin-based thermoplastic elastomers and the like are particularly preferable.

  A homopolymer or copolymer mainly composed of polypropylene is also preferable, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and an α having 2 to 20 carbon atoms other than propylene and having a polypropylene crystal part. -Olefins. In addition, a propylene-α-olefin copolymer containing 15 mol% or more of a comonomer of ethylene, butene-1,4-methylpentene-1, hexene-1, or octene-1 is also preferable.

  The polyolefin-based thermoplastic elastomer is preferably a mixture of isotactic polypropylene in the hard segment and atactic polypropylene in the soft segment in a weight ratio of 80:20.

  The polyolefin resin may be formed into a film by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like.

When forming the base material layer, the thickness (thickness) of the base material layer is set so that the thickness of the transparent resin layer described later is twice or more the thickness of the base material layer. Ie, T the thickness of the substrate layer _B, and the thickness of the transparent resin layer in the case of the T _R, to set the thickness of the substrate layer such that the T _R / T _B ≧ 2. Here, hereinafter, T _R / T _B is also referred to as a transparent resin layer ratio in the present specification. If the transparent resin layer ratio is less than 2 (T _R / T _B <2), the transparent resin layer absorbs most of the energy from infrared rays, while the base material layer has little (infrared) energy. Can only absorb. Therefore, since the base material layer does not soften so much, embossing of the base material layer becomes unsatisfactory, and as a result, overall excellent embossing property may not be obtained. The transparent resin layer ratio is preferably 5 to 7.5.

  The thickness of the base material layer is preferably about 60 to 100 μm on the assumption that the transparent resin layer ratio is 2 or more.

  An additive may be blended in the base material layer as necessary. Examples of the additive include a filler such as calcium carbonate and clay, a flame retardant such as magnesium hydroxide, an antioxidant, a lubricant, a foaming agent, and a colorant (see below). Moreover, the compounding quantity of an additive can be suitably set according to a product characteristic.

  It does not specifically limit as a coloring agent, Well-known coloring agents, such as a pigment and dye, can be used. For example, titanium white, zinc white, petal, vermilion, ultramarine blue, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments; isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indanthrene Organic pigments (including dyes) such as blue RS and aniline black; metal pigments such as aluminum and brass; pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate. The coloring aspect of the base material layer includes transparent coloring and opaque coloring (hiding coloring), and these can be arbitrarily selected. For example, when the ground color of an adherend (a base material on which a decorative sheet is pasted, such as a wooden base material) is concealed, opaque coloring may be selected. On the other hand, in order to make the ground pattern of the adherend visible, transparent coloring may be selected.

  One or both surfaces of the base material layer may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, etc., as necessary. For example, when performing corona discharge treatment, the surface tension of the substrate layer surface may be 30 dyne or more, preferably 40 dyne or more. The surface treatment may be performed according to a conventional method for each treatment.

  A primer layer may be provided on one side or both sides of the base material layer as necessary.

  A primer layer can be formed by apply | coating a well-known primer agent to the single side | surface or both surfaces of a base material layer. Examples of the primer agent include a urethane resin primer agent made of acrylic modified urethane resin, a primer agent made of urethane-cellulose resin (for example, a resin made by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton), and the like. Is mentioned.

The application amount of the primer layer is not particularly limited, but is usually 0.1 to 20 g / m ² , preferably about 0.5 to 10 g / m ² .

Pattern Pattern Layer The decorative sheet of the present invention has a pattern pattern layer.

  The design pattern layer imparts design properties with a desired design to the decorative sheet, and the type of design is not particularly limited. Examples thereof include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern.

  The method for forming the pattern layer is not particularly limited. For example, a colored ink or coating obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin. What is necessary is just to form by the printing method etc. which used the agent.

  Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments. Organic pigments such as aluminum powder, metal powder pigments such as bronze powder, pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants can be used singly or in combination of two or more. These colorants may further contain fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.

  Examples of the binder resin include acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum Resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like. These resins can be used singly or in combination of two or more.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, acetic acid-2-methoxyethyl, acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc. Containing organic solvent; inorganic solvents such as water. These solvents (or dispersion media) can be used alone or in combination of two or more.

  Examples of the printing method used for forming the pattern layer include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method. When forming a solid pattern pattern layer, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating Various coating methods such as a coating method may be mentioned. In addition, the hand-drawn method, the ink-sink method, the photographic method, the transfer method, the laser beam drawing method, the electron beam drawing method, the metal partial evaporation method, the etching method, etc. may be used or combined with other forming methods. Good.

  The thickness of the pattern layer is not particularly limited and can be appropriately set according to the product characteristics, but the thickness after drying (layer thickness) is about 0.1 to 20 μm.

Colored concealment layer A colored concealment layer may be formed as a base of the pattern layer or in place of the pattern layer. The colored masking layer is provided when it is desired to mask the ground color of the adherend from the front surface of the decorative sheet. Of course, when the base material layer is transparent, even when the base material layer is concealed and colored, it may be formed in order to stabilize the concealability.

  As the ink for forming the colored masking layer, an ink for forming a pattern layer and capable of masking coloring can be used.

  As a method for forming the colored concealing layer, a method that can be formed so as to cover the entire base material layer (entire solid surface) is preferable. For example, the roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating method and the like described above are preferable.

  The thickness of the colored hiding layer is not particularly limited and can be set as appropriate according to the product characteristics, but the thickness after drying is about 0.1 to 20 μm.

Transparent adhesive layer A transparent adhesive layer may be formed on the pattern layer. The transparent adhesive layer is not particularly limited as long as it is transparent, and includes any of transparent and colorless, colored and translucent. The transparent adhesive layer is formed in order to bond the pattern layer and the transparent resin layer.

  It does not specifically limit as an adhesive agent, A well-known adhesive agent can be used in the field of a decorative sheet.

  Examples of the adhesive known in the field of decorative sheets include thermoplastic resins such as polyamide resin, acrylic resin and vinyl acetate resin, and curable resins such as thermosetting urethane resin. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.

  For example, the adhesive layer is applied by applying an adhesive on the pattern layer (or on the base material layer so as to cover the pattern layer), drying, laminating a transparent resin layer, and then curing. Can be formed. Conditions such as drying temperature and drying time are not particularly limited, and may be set as appropriate according to the type of adhesive. The method of applying the adhesive is not particularly limited, and examples thereof include roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, and comma coating. The method can be adopted.

  Although the thickness of an adhesive bond layer is not specifically limited, The thickness after drying is 0.1-30 micrometers, Preferably it is about 1-20 micrometers.

Transparent resin layer The decorative sheet of the present invention has a transparent resin layer on the pattern layer.

  The transparent resin layer may be colored as long as it is transparent, and may be translucent as long as the pattern layer is visible.

  Examples of the resin component contained in the transparent resin layer include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-acrylic. Examples include acid ester copolymers, ionomers, polymethylpentene, acrylic acid esters, methacrylic acid esters, polycarbonates, and cellulose triacetates. Among these, olefin resins such as polypropylene are preferable, and polyolefin resins are more preferable. More preferably, it is a polyolefin resin having stereoregularity. When using an olefin resin, it is desirable to form a transparent resin layer by extruding a molten olefin resin.

  The thickness of the transparent resin layer is 120 μm or more. Thereby, the flaw resistance and abrasion resistance which are requested | required of a decorative sheet (especially decorative sheet for floors) can be ensured. The thickness of the transparent resin layer is preferably 350 to 800 μm, more preferably 400 to 600 μm.

  The transparent resin layer contains at least one infrared absorber selected from the group consisting of antimony-doped tin oxide and indium-doped tin oxide. By containing the infrared absorber (heat ray absorber) in the transparent resin layer, even if the thickness of the transparent resin layer is in the above range, the entire decorative sheet is efficiently warmed and softened without transmitting infrared rays. Can be made. Therefore, the embossing property which was excellent in the decorative sheet can be provided by the press by the embossing plate mentioned later. In addition, infrared rays emitted from heating devices and the like can be efficiently absorbed and stored, which leads to an improvement in indoor heating efficiency.

  The shapes of antimony-doped tin oxide (ATO) and indium-doped tin oxide (ITO) are not particularly limited, but are preferably fine particles. When the shape is fine particles, the average primary particle diameter is preferably about 1 to 100 nm.

  Examples of commercially available products of ATO that can be used in the present invention include SN-100P manufactured by Ishihara Sangyo Co., Ltd., ATO-P100 manufactured by Shanghai Hosho Nanotechnology Co., Ltd. and the like. Moreover, as a commercial item of ITO which can be used in the present invention, for example, ITO-P100 manufactured by Shanghai Hosho Nanotechnology Co., Ltd., ITO (ITO powder) manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd., and the like can be mentioned.

  Content of the said infrared absorber is 1-20 mass parts with respect to 100 mass parts of resin components which comprise a transparent resin layer. When the content of the infrared absorber is within the above range, the entire decorative sheet can be efficiently warmed and softened by infrared rays while maintaining the heat resistance of the decorative sheet. Therefore, the embossing property which was excellent in the decorative sheet can be provided by the press by the embossing plate mentioned later. In addition, infrared rays emitted from heating devices and the like can be efficiently absorbed and stored, which leads to an improvement in indoor heating efficiency.

  In the transparent resin layer, the filler, matting agent, foaming agent, flame retardant, lubricant, antistatic agent, antioxidant, ultraviolet absorber, light stabilizer, radical, etc. Various additives such as a scavenger and a soft component (for example, rubber) may be contained.

  The surface of the transparent resin layer on which the surface protective layer is formed is subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment as necessary. Also good. The surface treatment may be performed according to a conventional method for each treatment.

A primer layer for facilitating the formation of the surface protective layer may be provided on the primer layer transparent resin layer.

  The primer layer can be formed by applying a known primer agent to the transparent resin layer. Examples of the primer agent include a urethane resin-based primer agent composed of an acrylic-modified urethane resin and the like, and a resin-based primer agent composed of a block copolymer of acrylic and urethane.

The application amount of the primer agent is not particularly limited, but is usually about 0.1 to 20 g / m ² , preferably about 0.5 to 10 g / m ² .

A surface protective layer is formed on the surface protective layer transparent resin layer. The surface protective layer is not limited, but preferably contains at least one of an ionizing radiation curable resin and a two-component curable urethane resin as a resin component. Substantially those formed from these resins are preferred. When the surface protective layer is formed from a resin composition containing an ionizing radiation curable resin or a two-component curable urethane resin, the abrasion resistance, impact resistance, contamination resistance, scratch resistance, weather resistance, etc. of the decorative sheet Easy to increase.

  The ionizing radiation curable resin is not particularly limited, and prepolymers (including oligomers) and / or monomers containing radically polymerizable double bonds capable of undergoing a crosslinking reaction upon irradiation with ionizing radiation such as ultraviolet rays and electron beams. A transparent resin containing as a main component can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction is usually a cross-linking curing reaction.

  Specifically, as the prepolymer or monomer, a compound having in the molecule a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group. Is mentioned. Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferable. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group.

  Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Etc. These molecular weights are usually preferably about 250 to 100,000.

  As a monomer which has a radically polymerizable unsaturated group, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate etc. are mentioned as a monofunctional monomer, for example. Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra ( And (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

  Examples of the prepolymer having a cationic polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolac type epoxy compounds, and vinyl ether type resins such as fatty acid type vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those in which allyl alcohol is added to both ends of polyurethane by diol and diisocyanate.

  As the ionizing radiation used for curing the ionizing radiation curable resin, electromagnetic waves or charged particles having energy capable of causing a curing reaction of molecules in the ionizing radiation curable resin (composition) are used. Usually, ultraviolet rays or electron beams may be used, but visible light, X-rays, ion rays, or the like may be used.

  As the ultraviolet light source, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp can be used. As a wavelength of ultraviolet rays, 190 to 380 nm is usually preferable.

  As the electron beam source, for example, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Among these, those capable of irradiating electrons having energy of 100 to 1000 keV, preferably 100 to 300 keV are preferable.

  The two-component curable urethane resin is not particularly limited, but among them, a polyol component (such as acrylic polyol, polyester polyol, polyether polyol, and epoxy polyol) having an OH group as a main component and an isocyanate component (tolylene diene) that is a curing agent component. Isocyanate, hexamethylene diisocyanate, metaxylene diisocyanate and the like) can be used.

  The surface protective layer may contain at least one infrared absorber selected from the group consisting of the aforementioned ATO and ITO. The description of the ATO and ITO shapes, average primary particle size, commercial products, etc. is the same as described above.

  As for content of an infrared absorber, 1-10 mass parts is preferable with respect to 100 mass parts of resin components which comprise a surface protective layer.

  The surface protective layer may contain an anti-glare agent, a plasticizer, a stabilizer, a filler, a dispersant, a colorant such as a dye and a pigment, a solvent, and the like, if necessary. About the kind in case of containing a weathering agent and content, it is the same as that of the description in a transparent resin layer.

  The surface protective layer is, for example, after coating a resin composition containing an ionizing radiation curable resin or a two-component curable urethane resin on a transparent polypropylene resin layer by a known coating method such as gravure coating or roll coating. It can be formed by curing the resin. In the case of an ionizing radiation curable resin, the resin is cured by electron beam irradiation.

  The thickness of the surface protective layer is not particularly limited and can be appropriately set according to the characteristics of the final product, but is usually about 0.1 to 50 μm, preferably about 1 to 30 μm.

Backer layer Back surface of the pattern layer (if the base layer is on the back side of the pattern layer, back side of the base layer) Backer layer (to increase the scratch resistance or reduce the influence of the substrate) A synthetic resin layer) may be provided. In addition, the above scratch resistance refers to a dent scratch when a load is applied partially, and the decorative sheet of the present invention has sufficient scratch resistance without providing a backer layer, but a backer layer is provided. Thus, various performances such as scratch resistance can be further enhanced.

  As a method for forming the backer layer, extrusion molding of a molten resin is suitable, for example, extrusion molding using a T die is suitable.

  As a method of adhering the back side of the pattern layer or the base material layer and the backer layer, a method of adhering the base material layer and the backer layer obtained by extruding the molten resin by heat fusion, the pattern layer or The method etc. which adhere | attach by providing an adhesive bond layer (and also a primer layer as needed) between a base material layer and a backer layer, etc. are mentioned.

  Although it does not limit as resin which comprises a backer layer, a thermoplastic resin, for example, polyethylene (PE. In any case of low density polyethylene, linear low density polyethylene, medium density polyethylene, and high density polyethylene.), Polypropylene (PP), ethylene-α-olefin, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer Polymers and acid-modified products thereof, ionomers, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, amorphous polyethylene terephthalate (A-PET), polyalkylene terephthalate having high heat resistance [for example, Polyethylene terephthalate in which a part of ethylene glycol is substituted with 1,4-cyclohexanedimethanol, diethylene glycol or the like, so-called trade name PET-G (manufactured by Eastman Chemical Company)], polybutylene terephthalate (PBT), polycarbonate, poly Examples include arylate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polyimide, polystyrene, polyamide, and ABS (acrylonitrile-butadiene-styrene copolymer). These resins can be used alone or in combination of two or more.

  The backer layer may be a foam. In this case, in addition to the scratch resistance, excellent heat insulating properties and a feeling of walking can be imparted.

  As a formation method when the backer layer is a foam, a conventionally known resin foaming method can be employed. For example, (1) a method in which a thermoplastic resin pellet or bead is impregnated with gas, heated and melted by an extruder, and foamed when exiting the die, and (2) a thermoplastic resin pellet or bead is extruded by an extruder. A method of heating and melting, injecting and kneading gas into the mold, and foaming when the die exits, (3) Pellet or beads of thermoplastic resin containing foaming agent is heated and melted with an extruder, and the die (4) A chemical foaming agent that generates gas by decomposing at a molding temperature with pellets of thermoplastic resin, by obtaining an unfoamed sheet at the time of exiting, and by foaming and crosslinking by heating or electron beam irradiation in post-processing Are mixed, heated and melted with an extruder, and foamed when exiting the die.

  Examples of the foaming agent include pyrolytic foaming agents such as azodicarbonamide, azobisisobutyronitrile, N—N′-dinitrosopentamethylenetetramine, oxybisbenzenesulfonylhydrazide, sodium bicarbonate, potassium bicarbonate, and the like. A microcapsule type foaming agent in which a thermally expanded gas such as hexane or isobutane is enclosed in a resin spherical shell such as acrylonitrile. The addition amount is preferably about 1 to 10 parts by mass with respect to 100 parts by mass of the resin component of the foam, and the expansion ratio is 5 to 15 times.

  The thickness of the backer layer can be appropriately set depending on the use of the final product, the method of use, etc., but generally it is preferably 100 to 800 μm. Among these, 400-600 micrometers is more preferable.

  If necessary, the backer layer may be subjected to known easy adhesion treatment such as corona discharge treatment, plasma treatment, degreasing treatment, surface roughening treatment, and the like on the adhesion surface. Further, a primer layer may be further provided on the back surface in consideration of adhesiveness with the adherend.

  In the present invention, by providing the backer layer, the scratch resistance can be enhanced and the influence of the adherend can be reduced. For example, the effect of unevenness existing on the surface of the adherend can be alleviated, and especially when the adherend is made of wood, the unevenness of polishing formed on the surface during sanding or the knots on the wood (so-called ducts) ) Can be mitigated. In particular, in the case of a decorative sheet having a low gloss, it is easy to be affected by the duck of the wood-based adherend. Therefore, it is preferable to reduce the influence of the duck by providing a backer layer.

Embossing An embossed pattern is formed on the outermost layer side of the decorative sheet of the present invention. In the present specification, the embossing means heating of the laminate and pressing (pressing) with an embossing plate, and after the embossing, a concavo-convex pattern by embossing is formed on the outermost layer side of the decorative sheet. .

As a method of forming an embossed pattern on the outermost layer side, the following (1) or (2):
(1) After forming a laminate having in order at least a transparent resin layer and a surface protective layer on the pattern layer, the whole laminate is heated and softened by radiating infrared rays from above the surface protective layer. Then, a method of forming an embossed pattern by pressing an embossed plate from above the surface protective layer of the laminate;
(2) After forming a laminate having at least a transparent resin layer on the pattern layer, the laminate is heated and softened by emitting infrared rays from above the transparent resin layer, and then the laminate. The embossed plate is pressed from above the transparent resin layer to form an embossed pattern on the transparent resin layer, and then a resin composition for forming a surface protective layer is applied on the transparent resin layer. Forming a surface protective layer having a pattern;
Etc. In the present invention, infrared rays (heat rays) include all of near infrared rays, middle infrared rays, and far infrared rays.

  As described above, the decorative sheet of the present invention contains at least one infrared absorber selected from the group consisting of a specific amount of ATO and ITO in the transparent resin layer, so that the decorative sheet does not transmit infrared rays. The whole can be efficiently warmed and softened. Therefore, the embossing property which was excellent in the decorative sheet can be provided by pressing with the embossing plate with respect to the said softened laminated body.

  An infrared lamp heater is generally used as the infrared source, and a carbon lamp, a Colts lamp, a halogen lamp, or the like can be used. In particular, near infrared lamps such as a Colts lamp and a halogen lamp are preferable from the viewpoint of energy efficiency.

  The laminated body is heated by emitting infrared rays. Although the said heating temperature will not be specifically limited if the outstanding uneven | corrugated embossed pattern can be shape | molded, For example, it can carry out so that a laminated body temperature may be 150-160 degreeC.

  The pressing by the embossing plate can be performed using a known single wafer type or rotary type embossing machine. Examples of the concavo-convex shape include a wood grain plate conduit groove, a stone plate surface unevenness (such as granite cleaved surface), a cloth surface texture, a satin texture, a grain, a hairline, a ridge line, and the like. After pressurizing with an embossing plate and forming an embossed pattern, it may be cooled.

≪Method 1 for manufacturing decorative sheet≫
The decorative sheet of the present invention is
(i) a laminate having at least a transparent resin layer and a surface protective layer in order on the design pattern layer,
(1) The thickness of the transparent resin layer is 120 μm or more,
(2) the transparent resin layer contains at least one infrared absorber selected from the group consisting of antimony-doped tin oxide and indium-doped tin oxide;
(3) Step 1 of heating the laminated body in which the content of the infrared absorber is 1 to 20 parts by mass with respect to 100 parts by mass of the resin component constituting the transparent resin layer, and
(ii) Step 2 of forming an embossed pattern on the laminate by pressing an embossed plate from above the surface protective layer of the laminate obtained in Step 1;
In order. Here, the said laminated body is the same as that of the decorative sheet of this invention except that the embossed pattern is not shaped.

  About description of each process, it is the same as that of the description in the above-mentioned decorative sheet.

≪Method for manufacturing decorative sheet 2≫
The decorative sheet of the present invention is
(i) a laminate having at least a transparent resin layer on the pattern layer,
(1) The thickness of the transparent resin layer is 120 μm or more,
(2) the transparent resin layer contains at least one infrared absorber selected from the group consisting of antimony-doped tin oxide and indium-doped tin oxide;
(3) Step 1, in which the laminate, in which the content of the infrared absorber is 1 to 20 parts by mass with respect to 100 parts by mass of the resin component constituting the transparent resin layer, is heated by infrared rays.
(ii) a step 2 of shaping an embossed pattern on the laminate by pressing an embossed plate from above the transparent resin layer of the laminate obtained in the step 1, and
(iii) Step 3 of forming a surface protective layer by applying a resin composition that forms a surface protective layer on the transparent resin layer
Can also be obtained by a production method including the following.

  About description of each process, it is the same as that of the description in the above-mentioned decorative sheet.

≪Cosmetic materials≫
The decorative sheet of the present invention can be made into a decorative material by bonding with various adherends. The material of the adherend is not particularly limited, and examples thereof include inorganic non-metallic materials, metallic materials, wood materials, and plastic materials.

  Specifically, in inorganic non-metallic systems, for example, papermaking cement, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), pulp cement, wood chip cement, asbestos cement, calcium oxalate, Non-ceramic ceramic materials such as gypsum and gypsum slag, ceramic materials such as earthenware, ceramics, porcelain, setware, glass, and glazing.

  In a metal system, metal materials (metal steel plate), such as iron, aluminum, and copper, are mentioned, for example.

  In the wood system, for example, a single board, plywood, particle board, fiber board, laminated timber and the like made of cedar, straw, firewood, lauan, teak and the like can be mentioned.

  In the plastic system, for example, resin materials such as polypropylene, ABS resin, and phenol resin can be used.

  The shape of such an adherend is not particularly limited, and may be a flat plate in consideration of installation on a flooring or the like.

  After joining with the adherend, for example, according to the characteristics of the final product, cutting, using a tenoner, applying a sword, applying a V-shaped groove, chamfering four sides, or the like may be performed.

  The decorative sheet of the present invention has a specific layer structure after containing a specific amount of a specific infrared absorber in a transparent resin layer having a specific thickness. Therefore, even if it is a case where embossing is given by the heating by infrared rays and the press by an embossing plate, it is excellent in heat storage and embossing moldability, ensuring abrasion resistance, transparency, and heat resistance.

It is a schematic diagram which shows the layer structure of the decorative sheet produced in Examples 1-8 and 10-11, and Comparative Examples 1-11. 6 is a schematic diagram showing a layer structure of a decorative sheet produced in Example 9. FIG. FIG. 4 is a schematic diagram showing a layer structure of a decorative sheet produced in Examples 12 and 13.

  The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
(Production of decorative sheet)
As a base material layer, a colored polypropylene layer (Art Ply, manufactured by Mitsubishi Plastics, Inc.) having a thickness of 80 μm was prepared.

  After applying corona discharge treatment to the front and back surfaces of the base material layer, a primer agent is applied to the back surface to form a back surface primer layer (thickness 2 μm). A wood grain pattern layer (thickness 2 μm) was formed on the surface. A polyester two-component curable adhesive (Seika Bond E-263 / C-75N, manufactured by Dainichi Seika Kogyo Co., Ltd.) was applied onto the pattern layer and dried to form an adhesive layer (thickness 5 μm). .

  Next, on the adhesive layer, 100 parts by mass of transparent polypropylene (Novatech PP, manufactured by Nippon Polypro Co., Ltd.) and 1 part by mass of infrared absorber (ATO fine particles SN-100P, manufactured by Ishihara Sangyo Co., Ltd.) are used as a T-die extruder. Was heated and melt-extruded to form a transparent resin layer (thickness 400 μm).

  Next, the front surface of the transparent resin layer was subjected to corona discharge treatment, and then a primer layer (primer layer for forming a surface protective layer, thickness 2 μm) was formed on the transparent resin layer. A surface protective layer (thickness: 15 μm) was formed on the primer layer by coating and drying an ionizing radiation curable resin by a gravure method.

  The surface protective layer is heated and melted (150 to 160 ° C.) until the laminate is softened by emitting infrared rays from above the surface protective layer with an infrared lamp (halogen heater manufactured by Metro Electric Industry Co., Ltd.), and then the surface protective layer. Embossing was carried out by pressing the embossed plate from above to obtain a decorative sheet having an uneven pattern.

Examples 2-8 and 10-11, and Comparative Examples 1-11
Example 1 except that (a) the thickness of the base material layer, (b) the content of the infrared absorber, (c) the component of the infrared absorber, (d) the thickness of the transparent resin layer, etc. are appropriately changed. In the same manner, a decorative sheet was obtained. The above (a) to (d) are as shown in Table 1 or 2. In addition, when using ITO as an infrared absorbing agent, ITO-P100 manufactured by Shanghai Hosho Nanotechnology Co., Ltd. was used.

Example 9
100 parts by mass of transparent polypropylene (Novatech PP, manufactured by Nippon Polypro Co., Ltd.) and 10 parts by mass of infrared absorber (ATO fine particle SN-100P, manufactured by Ishihara Sangyo Co., Ltd.) are heated and melt extruded using a T-die extruder, and are transparent. A resin layer (thickness 400 μm) was formed.

  Next, corona treatment was performed on both surfaces of the transparent resin layer, and a primer layer (thickness 2 μm) was formed on the back surface. A woodgrain pattern layer (thickness: 2 μm) was formed on the back surface of the primer layer.

  Subsequently, in the same manner as in Example 1, formation of the surface protective layer forming primer layer and the surface protective layer, and embossing were performed. As a result, a decorative sheet having an uneven pattern was obtained.

Examples 12 and 13
Resin for forming a surface protective layer comprising an ionizing radiation curable resin and an infrared absorber (ATO fine particle SN-100P, manufactured by Ishihara Sangyo Co., Ltd.) on the surface protective layer forming primer layer instead of the ionizing radiation curable resin. A decorative sheet was obtained in the same manner as in Example 1 except that the surface protective layer was formed by coating and drying the composition. The content of the infrared absorber was as shown in Table 3.

(Production of cosmetic materials)
Application of water-based emulsion type two-component curable adhesive (BA-10 / BA-11B, Rikabond, Chuo Rika Kogyo Co., Ltd.) on wood base (MDF, 2.7mm, manufactured by Hokushin Co., Ltd.) / m ² ). In a state where the adhesive was wet, the wood base material and each of the decorative sheets were bonded together, and then press holding was performed. Thereby, a cosmetic material was obtained. In addition, the said bonding was performed so that the said adhesive agent coating surface and the back surface primer layer of a decorative sheet might contact | connect.

(Evaluation of decorative sheet or cosmetic material)
≪Emboss fastness (emboss moldability) ≫
First, the gloss value of the outermost surface of each decorative sheet was measured. Next, each decorative sheet was immersed in glycerin heated to 130 ° C. for 30 seconds, and then the gloss value of the outermost surface of the decorative sheet was measured again. In measuring the gloss value, a gloss meter PG-3D (angle 60 °) manufactured by Nippon Denshoku Industries Co., Ltd. was used. This measurement conforms to JIS Z8741.
The evaluation criteria were as follows. In the following evaluation criteria, the gloss value of the decorative sheet before immersion and G _B, the gloss value of the decorative sheet after immersion and G _A. It can be said that the closer G _A is to G _B , the better the embossing fastness is because there is less disappearance of the uneven pattern.
◎: _{G A} is in the range of _{G B ± G B × 10%} ○: G A is the outside of the _{G B ± G B × 10%} , G B ± G B × 20% within the range in a △: _{G a} is the outside of the _{G B ± G B × 20%} , × is in the range of _{G B ± G B × 30%} : G a is, _{G B} ± _{G B} × 30% Out of range

≪Abrasion resistance≫
The test was conducted in accordance with the JAS flooring wear A test. Specifically, a Taber abrasion tester was used for each decorative material, and the number of rotations when the pattern of each decorative material began to be taken was measured. The evaluation criteria were as follows. In the above test, the rotation was performed under the conditions of polishing paper S-42, load of 1000 g (including one wheel load of 500 g, including a rubber disk load).
◎: The number of rotations when the pattern starts to be taken is more than 2000 times. ○: The number of rotations when the pattern starts to be taken is more than 1500 times and less than 2000 times. △: When the pattern starts to be taken. The number of rotations is more than 1000 times and 1500 times or less. X: The number of rotations when the pattern starts to be taken is more than 500 times and 1000 times or less. XX: The number of rotations when the pattern starts to be taken is 500. Less than

≪Transparency (HAZE) ≫
Using a direct reading haze meter manufactured by Toyo Seiki Seisakusho Co., Ltd., only the transparent resin layer of each cosmetic material was put into the apparatus and the haze was measured. The evaluation criteria were as follows.
◎: Haze is less than 1 ○: Haze is 1 or more and less than 5 △: Haze is 5 or more and less than 10 ×: Haze is 10 or more

≪Heat storage ability≫
Each cosmetic material was placed 50 cm away from the infrared heater (output 500 W), and each cosmetic material was heated with the infrared heater for 30 seconds. The rise value of the surface temperature of each cosmetic material was measured. The evaluation criteria were as follows.
◎: Increase in surface temperature is 10 ℃ or more ○: Increase in surface temperature is 5 ℃ or more and less than 10 ℃ △: Increase in surface temperature is 1 ℃ or more and less than 5 ℃ ×: Increase in surface temperature is less than 1 ℃

≪Heat resistance≫
Each cosmetic material was placed 50 cm away from the infrared heater (output 500 W), and each cosmetic material was heated with the infrared heater for 30 minutes. Subsequently, the heat resistance of each decorative material was evaluated by evaluating the impact resistance of each heated decorative material using a DuPont impact tester. Specifically, a 500 g load weight is dropped from a height of 30 cm onto a 1/2 inch diameter shaft using a DuPont impact tester on each of the heated cosmetic materials. It evaluated by measuring the amount of dents. For reference, the above impact resistance against a color floor (room temperature) with a veneer (approx. 0.25 mm) on a plywood (approx. 11.8 mm) and UV coating (0.02 mm) on it. As a result of the test, the dent amount is 500 to 600 μm.
A: The amount of dent is 300 μm or less. ○: The amount of dent is larger than 300 μm and less than 500 μm. Δ: The amount of dent is larger than 500 μm and less than 600 μm.

(* 1): Example 11 indicates that 5 parts by mass of ATO fine particles and 5 parts by mass of ITO fine particles are contained as infrared absorbers.

1. Back primer layer
2. Base material layer
3. Pattern pattern layer
4. Transparent adhesive layer
5. Transparent resin layer
6. Surface protective layer

Claims (6)

A decorative sheet having at least a transparent resin layer and a surface protective layer in order on the pattern layer,
(1) The thickness of the transparent resin layer is 120 μm or more,
(2) the transparent resin layer contains at least one infrared absorber selected from the group consisting of antimony-doped tin oxide and indium-doped tin oxide;
(3) The content of the infrared absorber is 1 to 20 parts by mass with respect to 100 parts by mass of the resin component constituting the transparent resin layer,
(4) Embossed pattern is formed on the outermost layer side,
A decorative sheet characterized by that. A base material layer is formed on the back surface of the pattern layer,
The thickness of the transparent resin layer is at least twice the thickness of the base material layer,
The decorative sheet according to claim 1.   The decorative sheet according to claim 1 or 2, wherein the resin component constituting the surface protective layer is an ionizing radiation curable resin.   The decorative sheet according to any one of claims 1 to 3, wherein the surface protective layer contains at least one infrared absorber selected from the group consisting of antimony-doped tin oxide and indium-doped tin oxide.   The decorative sheet according to any one of claims 1 to 4, wherein the resin component constituting the transparent resin layer is an olefin resin.   A decorative material obtained by laminating the decorative sheet according to any one of claims 1 to 5 on an adherend.

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